CN112760096A - Design method and application of fluorescent quenching array sensor based on cadmium telluride quantum dots - Google Patents
Design method and application of fluorescent quenching array sensor based on cadmium telluride quantum dots Download PDFInfo
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- C09K11/881—Chalcogenides
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- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
本发明提供了一种基于碲化镉量子点荧光猝灭阵列传感器的设计方法及应用，以不同配体修饰的碲化镉量子点为传感元件，利用荧光信号差异的互补特性构建了荧光传感器阵列。该传感器能对己酸、乙酸、乳酸、丁酸、庚酸5种有机羧酸进行准确地定性判别与定量分析，并被广泛用于富含有机羧酸样品的在线识别监测。本发明基于四种不同配体修饰的碲化镉量子点开发的量子点传感阵列对有机酸的识别与定量分析能力强；响应速度快。相比于传统以多种有机染料组建的阵列传感器，该阵列传感具有操作简便、成本低廉、快速高效且容易实现在线可视化检测。该荧光传感器对其他富含有机羧酸的多组分复杂样品(如白酒)的鉴别具有实际的应用价值。
The invention provides a design method and application of a fluorescent quenching array sensor based on cadmium telluride quantum dots. The cadmium telluride quantum dots modified with different ligands are used as sensing elements, and the fluorescent sensor is constructed by utilizing the complementary characteristics of the difference of fluorescent signals. array. The sensor can accurately qualitatively discriminate and quantitatively analyze five organic carboxylic acids, including caproic acid, acetic acid, lactic acid, butyric acid and heptanoic acid, and is widely used for online identification and monitoring of samples rich in organic carboxylic acids. The quantum dot sensing array developed based on the cadmium telluride quantum dots modified by four different ligands has strong ability to identify and quantitatively analyze organic acids, and has fast response speed. Compared with the traditional array sensor composed of a variety of organic dyes, the array sensor has the advantages of simple operation, low cost, fast and efficient, and easy to realize online visual detection. The fluorescence sensor has practical application value for the identification of other multi-component complex samples rich in organic carboxylic acids (such as liquor).
Description
Technical Field
The invention relates to a metal quantum dot sensing array, in particular to a design method and application of a fluorescent quenching array sensor based on cadmium telluride quantum dots, which can be used for qualitative and quantitative analysis of caproic acid, acetic acid, lactic acid, butyric acid and heptanoic acid. Belongs to the field of nano technology and food detection.
Background
Organic acid in food is an important flavor substance, and the organic acid in the food is mainly derived from food raw materials, generated in a fermentation process and added in a production and processing process, wherein the type and the content of the organic acid have great influence on the flavor and the efficacy of the food. For example, organic acids, as the most important taste agent of white spirits, play a significant role in various white spirits. Short-chain organic acids in the wine mainly comprise acetic acid, lactic acid, butyric acid, heptanoic acid and caproic acid, and the acetic acid has the effects of helping digestion, sterilizing and resisting viruses, reducing blood fat and the like; lactic acid is an organic acid necessary for human body, can prevent cell aging, and has the effects of sterilization, virus resistance and the like; butyric acid has the functions of inhibiting the growth and reproduction of tumor cells and the like. The type and proportion of the acid have decisive effect on the body and style of the white spirit. Therefore, the discrimination analysis of the type and the content of the organic acid in the food has important significance for the food quality detection. Most of traditional methods for detecting organic acids in food are chromatographic methods, and the instrumental detection method has the advantages of strong recognition capability of organic acids in complex mechanisms, high detection sensitivity and the like, but has the limitations of complex operation, high cost and the like. Therefore, a method for detecting organic acids in food rapidly, accurately and efficiently needs to be developed.
Optical sensor arrays are a simple and fast method of identifying complex mixtures based on multi-channel color or fluorescence changes. The fluorescent and colorimetric chemical sensor array has the characteristics of wide response range, high sensitivity and the like, compared with the traditional single-point response mode, the array sensor provides more abundant response signals, and improves the detection specificity, so the fluorescent and colorimetric chemical sensor array can be used for detecting a multi-component complex system of food. Compared with the traditional organic fluorescent dye molecules, the quantum dots have excellent photoelectric characteristics of good optical stability, high quantum yield, long fluorescence life and the like, and are widely researched in the field of biochemical sensing. By adjusting the composition, the size and the surface ligand structure of the nano particles, different photoelectric characteristics of the quantum dots are easily realized, and an extension strategy is provided for constructing a sensor array.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: a design method for constructing a quantum dot fluorescence sensing array based on four different ligand-modified cadmium telluride quantum dots is provided, the array is simple and convenient to manufacture, and can be used for qualitative discrimination and quantitative analysis of 5 different organic carboxylic acids.
The technical scheme adopted by the invention for solving the problems is as follows: a design method of a fluorescent quenching array sensor based on cadmium telluride quantum dots comprises the following specific steps:
(1) cadmium chloride and a mercapto group-containing ligand were dissolved in ultrapure water (molar mass ratio of cadmium chloride to ligand was 1: 1), and stirred at room temperature for 15 minutes. The pH was adjusted to different values (9.70, 11.00,10.00,5.50 for N-acetyl-L-cysteine, thioglycolic acid, glutathione, mercaptoethylamine ligands, respectively) with sodium hydroxide solution or hydrochloric acid solution depending on the ligand, and stirred for 15 minutes under nitrogen atmosphere. Adding sodium tellurite and cadmium chloride: the molar mass ratio of the sodium tellurite is 1: 0.2, adding sodium borohydride, cadmium chloride: the molar mass ratio of sodium borohydride is 3: and 4, introducing nitrogen and stirring for 10 minutes. And finally, putting the stirred solution into an oil bath at 100 ℃, and stirring for reaction until the fluorescence of the quantum dot solution is orange yellow or yellow-green. Cooling to room temperature, adding ethanol into the quantum dot solution and absolute ethyl alcohol according to the volume ratio of 1:3, standing for 30 minutes, centrifuging at the rotating speed of 8000rpm for 15 minutes, washing, dissolving the precipitate in absolute ethyl alcohol, repeating the centrifugal purification for three times, and refrigerating for later use, wherein the dosage of the absolute ethyl alcohol for three times is the same.
(2) Preparing 0.1mmol/L-0.8mmol/L of five organic acids of caproic acid, acetic acid, lactic acid, butyric acid and heptanoic acid by using ethanol, adding 990 mu L of prepared organic acid sample into the diluted 100 times quantum dot solution, keeping the quantum dot solution in a fluorescence quenching state, uniformly mixing, standing for 10 minutes, and measuring the fluorescence intensity. The addition of different organic acids causes the fluorescence intensity of the quantum dots to decrease to different degrees. And (3) respectively testing and recording spectral data of different quantum dots and different organic acid responses, measuring each sample in parallel for 6 times, and acquiring 3 groups of fluorescence spectral data each time.
(3) And (3) taking different quantum dots as sensing elements to establish a multi-channel fluorescence sensing array sensor.
Further, the fluorescence spectrum determination conditions in the step (2) are that the emission wavelength measurement range is 500-650nm, the excitation wavelength is 340nm, and the slits of the excitation wavelength and the emission wavelength are 10 nm.
Further, the concentration of quantum dots in each channel in the array sensor is the same.
The invention also provides application of the fluorescent array sensor based on the cadmium telluride quantum dots in qualitative discrimination and quantitative analysis of caproic acid, acetic acid, lactic acid, butyric acid and heptanoic acid.
Further, the concentration range of the caproic acid, the acetic acid, the lactic acid, the butyric acid and the heptanoic acid is 10 mu mol/L-80 mu mol/L.
Further, a sample to be detected is added in each channel of the array sensor in parallel for reaction, after the reaction, the fluorescence intensity is measured under the condition that the excitation wavelength is 340nm, the type of the organic acid sample is distinguished, and the fluorescence full spectrum is analyzed through a partial least square regression method, so that the five acids are quantitatively analyzed.
Further, the conditions for carrying out the reaction by adding the organic acid sample in parallel in each reaction were room temperature reaction for 10 minutes.
Compared with the existing sensing method, the method has the advantages and beneficial effects that:
the water-soluble quantum dot developed by the invention has simple and convenient synthesis process and low manufacturing cost. The quantum dot sensing array developed based on the cadmium telluride quantum dots modified by four different ligands has strong capability of identifying and quantitatively analyzing organic acids; the response speed is high. Compared with the traditional array sensor constructed by multiple organic dyes, the array sensor has the advantages of simple and convenient operation, low cost, high speed and high efficiency and is easy to realize online visual detection. The fluorescence sensor has practical application value in the identification of other multi-component complex samples (such as white spirit) rich in organic carboxylic acid.
Drawings
FIG. 1 is a flow chart of a method for cadmium telluride quantum dot based sensing array design and application thereof in accordance with the present invention.
Fig. 2 is a linear discriminant analysis diagram of the quantum dot array for 5 different organic acids.
Fig. 3(a) -3 (E) are graphs correlating actual and predicted acid concentrations based on the response fluorescence spectra of acids and quantum dots in the PLSR model. (A) Caproic acid; (B) lactic acid; (C) acetic acid; (D) butyric acid; (E) heptanoic acid.
FIG. 4 shows fluorescence response patterns F/F0 obtained from responses of different quantum dots and 30 kinds of white spirit (F0 and F are fluorescence intensities of quantum dot solutions before and after white spirit addition, respectively).
Fig. 5 is a schematic diagram of a variable information extraction process of a quantum dot sensor array.
FIG. 6 is a linear discriminant analysis diagram of a quantum dot array on 12 representative white spirit products with different odor types.
Fig. 7(a) and 7(B) are linear discriminant analysis graphs of quantum dot arrays for 30 branded white spirit products, (fig. 7(B) is an enlarged image of portion B in fig. 7 (a)).
FIG. 8 is a linear discriminant analysis diagram of quantum dot arrays for 3 different Luzhou Laojiao aged wine products.
Fig. 9 is a linear discriminant analysis diagram of the quantum dot array for 6 Luzhou Laojiao liquor products in different years.
Detailed Description
The present invention will be further described in detail with reference to specific examples below by the applicant to enable those skilled in the art to more clearly understand the present invention, but the present invention is not limited to the above examples. The following takes the identification of different commercial white spirits (different flavors, brands, qualities and years) as an embodiment, and the technical scheme of the invention is further explained in detail by combining the accompanying drawings.
Example (b):
the chemicals and solvents used in the examples were all analytical grade. The stirring mode adopts a magnetic stirrer. The concentration of the quantum dots in each column of the sensing array is the same, and the concentration of the quantum dots is determined by the yield of the quantum dots. The fluorescence spectrum measurement conditions are all emission wavelength of 500-650nm, excitation wavelength of 340nm, the detection condition of fluorescence spectrophotometry is excitation voltage of 400V, the slits of the excitation wavelength and the emission wavelength are 10nm, and the test is completed in a cuvette of 1 × 1 cm.
The invention aims to develop a method for quickly and accurately identifying commercial white spirit based on a quantum dot sensing array, which comprises the following implementation steps as shown in figure 1.
(1) Preparing cadmium telluride quantum dots modified by different ligands:
cadmium chloride (0.1650g, 0.9mmol) and a mercapto ligand (0.9mmol) were dissolved in 300mL of ultrapure water, stirred at room temperature for 15 minutes, after which the pH of the solution was adjusted to the corresponding values (9.70, 11.00,10.00,5.50 for N-acetyl-L-cysteine, thioglycolic acid, glutathione, mercaptoethylamine ligand, respectively) with 1mol/L sodium hydroxide solution, and then stirred under nitrogen atmosphere for 15 minutes. Stable sodium tellurite is used as a tellurium source, sodium tellurite (0.0399g,0.18mmol) is added, sodium borohydride (0.0540g,1.2mmol) is added, and stirring is carried out for 10 minutes. Finally, the solution was put into an oil bath to react under the conditions shown in Table 1. And cooling to room temperature to obtain the NAC @ CdTe quantum dot fluorescent probe. Different ligand quantum dot solutions were obtained according to the same molar mass ratio (cadmium chloride: ligand: sodium tellurite: 1: 0.2) from the synthesis conditions of table 1.
Purifying the cadmium telluride quantum dot solution: and cooling the synthesized quantum dot solution to room temperature, adding ethanol into the quantum dot solution according to the volume ratio of 1:3 of the quantum dot solution to absolute ethyl alcohol, standing for 30 minutes, centrifuging at the rotating speed of 8000rpm for 15 minutes, washing, dissolving the precipitate in absolute ethyl alcohol, performing centrifugal purification for three times, and refrigerating at 4 ℃ for later use, wherein the dosage of the absolute ethyl alcohol for three times is the same.
TABLE 1 Synthesis conditions of cadmium telluride quantum dots modified by different ligands
| QDs | NAC@CdTe | TGA@CdTe | MA@CdTe | GSH@CdTe |
| pH | 9.70 | 11.00 | 5.50 | 10.00 |
| T/℃ | 100 | 100 | 100 | 90 |
| t/ |
2 | 6 | 2 | 6 |
| Apex/nm | 586 | 550 | 562 | 577 |
(2) And designing and constructing a cadmium telluride quantum dot sensing array. Different ligands are used for modifying water-soluble cadmium telluride quantum dots as fluorescent sensing elements to form a multi-channel array sensor. The reaction is carried out at normal temperature, and the specific sample adding sequence is 990uL of diluted quantum dot solution +10uL of organic acid, and ethanol is used as a control. The fluorescence spectra were obtained by measuring the fluorescence intensity of the quantum dot solutions in a 1X 1cm cuvette.
The application of the multi-channel array sensor based on quantum dot fluorescence quenching in the aspects of identifying organic acid samples and the like is as follows: adding an organic acid sample in parallel into each channel of the array sensor for reaction, adding an organic acid sample in parallel into each channel for reaction, wherein the reaction condition is usually room temperature mixing reaction for 10 minutes (each column is a quantum dot solution, and different organic acids are added in parallel into each row), and testing the fluorescence intensity of the blank quantum dot solution and the fluorescence intensity of the quantum dot solution after the organic acid is added. And (3) introducing chemometrics Linear Discriminant Analysis (LDA) to extract fluorescence spectrum characteristic information, and realizing the discrimination of the organic acid sample species. In addition, by adding organic acid samples with different concentrations, after the spectral information of the organic acid samples is obtained through testing, accurate judgment of the organic acid samples is achieved (figure 2), and responses of four quantum dots and 5 organic acids are tested. The experiment was repeated 6 times in parallel, three sets of fluorescence spectrum data were recorded each time, and finally 18 sets of fluorescence spectrum data were obtained. The accuracy of the cross validation of the cutting method is 100%, which is shown in table 2. The fluorescence ensemble spectrum was analyzed by partial least squares regression to quantitatively analyze 5 acids of hexanoic acid, acetic acid, lactic acid, butyric acid, and heptanoic acid, as shown in fig. 3(a) -3 (E). The concentrations of the 5 organic acids in the sample to be tested need to be diluted to 10-80 mu mol/L.
TABLE 25 organic acid knife-cutting classification discrimination matrix
The concentration of cadmium telluride quantum dots of each channel in the quantum dot array sensor is the same, the concentration is determined by quantum yield of quantum dots fluorescence, the detection condition of fluorescence spectrophotometry is excitation voltage 400V, the slit of excitation wavelength and emission wavelength is 10nm, and the test is completed in a cuvette of 1 multiplied by 1 cm. The original fluorescence intensity of the quantum dots is about 1600-2000.
(3) And (3) testing the fluorescent response of different white spirits to 4 kinds of quantum dot solutions:
the organic acid is the most important taste agent of the white spirit, the short-chain organic acid in the white spirit mainly comprises acetic acid, caproic acid, lactic acid, butyric acid, heptanoic acid and the like, and the types and the proportions of the acids have decisive effects on the spirit body and the style of the white spirit. And (3) constructing a quantum dot fluorescent sensor array for testing and identifying the white spirit by using the acid-sensitive quantum dots obtained in the step (1). The 10uL quantum dot solution is diluted by 100 times until the fluorescence intensity at the emission wavelength of each quantum dot is about 1600 to 2000, which is the original fluorescence intensity F0. Diluting the white spirit sample by 10 times with 52% alcohol to be used as a test sample, adding 10uL of the white spirit test sample into 990uL of diluted quantum dot solution, uniformly mixing, testing the fluorescence intensity after 10 minutes, and recording the spectrum data. And (4) adding different white spirits in sequence, and testing the corresponding fluorescence spectra according to the method.
Then, according to the same method, the response of other three quantum dots to the white spirit is tested. The above experiment was repeated six times, three sets of fluorescence spectrum data were recorded each time, and the final spectrum data was the average of 18 data. The fluorescence intensity of the quantum dot solution is reduced with different degrees after different white spirits are added.
The ratio of the fluorescence intensity (F) of the quantum dots after the white spirit is added to the original fluorescence intensity (F0) of each quantum dot at the emission wavelength is used as the ordinate, different white spirits are used as the abscissa, and the fluorescence response modes obtained by the response of different quantum dots and 30 white spirits are obtained, and as shown in FIG. 4, each white spirit sample has a unique fluorescence label.
In this example, 30 representative commercial wines and 6 year wines were selected as test samples (tables 3 and 4).
Table 330 detailed information of commercial white spirit samples
Table 46 details of liquors in different storage years
(3) Construction of a quantum dot fluorescence sensing array:
based on the cross reaction and response information complementary characteristics of quantum dots of different ligands and white spirit, quantum dots are used as sensing elements to establish a fluorescence sensor array, the fluorescence intensity of quantum dot solutions of all channels after different white spirit samples are added is detected and recorded, and the experiment is independently repeated for 6 times.
(4) Identification of different flavors, brands, qualities and years of white spirit:
the training matrix (4 quantum dots x number of samples x 18 replicates) was converted to a standard score and the fluorescence peak was analyzed by SYSTAT13.2 with LDA. As shown in fig. 5, the quantum dot sensing array matrix data is further analyzed to obtain a corresponding liquor product linear discriminant analysis diagram. FIG. 6 is a linear discriminant analysis chart obtained by response of quantum dot arrays to different types of white spirits (strong-flavor type, fen-flavor type, maotai-flavor type, mixed-flavor type, rice-flavor type, phoenix-flavor type, sesame-flavor type, fermented soybean-flavor type, special-flavor type, medicinal-flavor type, white spirit type and strong-flavor type), and horizontal and vertical coordinates represent factor contribution rates.
TABLE 5 white spirit knife classification and discrimination matrix with different flavor
As shown in Table 5, the array has 100% accuracy in distinguishing white spirits with different flavor types. Fig. 7(a) and 7(B) show linear discriminant analysis diagrams obtained by analyzing different brands of white spirits (luzhou laojiao, shui jing, jiannan chun, wuliangye, gujing tribute wine, yanghe, fen wine, tianyoude highland barley, baofeng lotus goblet, cowry mountain biguotou, hong xing biguotou, jiangbai, maotai, lang wine, kouzui, baiyunrong, guilin sanhua, west phoenix, Jing zhi, Yu Bingshao, Site, dong wine, laobaigan, drunkard) (fig. 7(B) is an enlarged image of part B in fig. 7 (a)).
TABLE 6 knife-cutting classification and discrimination matrix for commercial white spirits of different brands
As shown in Table 6, the liquor sample L12 (Yanghe micromolecule) was misjudged to be L11 (blue of Yanghe dream), the cross discrimination accuracy of other knife cutting methods is 100%, and the total discrimination accuracy obtained by array recognition of different brands of liquor is 99.8%.
TABLE 7 knife-cut classification discrimination matrix for different cellar ages of Bainian Luzhou Laojiao
| LZ-30Y | LZ-60Y | LZ-90Y | The accuracy rate% | |
| LZ- |
18 | 0 | 0 | 100 |
| LZ- |
0 | 18 | 0 | 100 |
| LZ- |
0 | 0 | 18 | 100 |
| Total | 18 | 18 | 18 | 100 |
The linear discriminant analysis graph obtained by quantum dot array recognition of white spirits of different qualities (30 years, 60 years and 90 years old wine in Bainian Luzhou Laojiao) is shown in FIG. 8, 3 kinds of Laojiao wine can be distinguished well, and the discrimination accuracy is 100% as shown in Table 7.
TABLE 8 knife classification discrimination matrix for different years of Luzhou Laojiao
| 3Y | 4Y | 5Y | 7Y | 9Y | 12Y | The accuracy | |
| 3Y | |||||||
| 18 | 0 | 0 | 0 | 0 | 0 | 100 | |
| |
0 | 18 | 0 | 0 | 0 | 0 | 100 |
| |
0 | 0 | 18 | 0 | 0 | 0 | 100 |
| |
0 | 0 | 0 | 18 | 0 | 0 | 100 |
| |
0 | 0 | 0 | 0 | 18 | 0 | 100 |
| |
0 | 0 | 0 | 0 | 0 | 18 | 100 |
| Total of | 18 | 18 | 18 | 18 | 18 | 18 | 100 |
The linear discriminant analysis graph for identifying different qualities of different-year white spirits (3 years, 4 years, 5 years, 7 years, 9 years and 12 years of Luzhou Laojiao wine) by the array is shown in FIG. 9. The white spirits of different storage years can be distinguished according to the storage time, and the accuracy rate is judged by the knife cutting method, which is shown in table 8. The above shows that the fluorescence sensing array provided by the invention can accurately distinguish and analyze Chinese white spirit.
The above-described embodiments are intended to illustrate rather than to limit the invention, and any modifications and variations of the present invention are within the spirit of the invention and the scope of the appended claims.
Claims (7)
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| US20080246006A1 (en) * | 2005-03-31 | 2008-10-09 | Agency For Science, Technology And Research | Cdte/Gsh Core-Shell Quantum Dots |
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| US20080246006A1 (en) * | 2005-03-31 | 2008-10-09 | Agency For Science, Technology And Research | Cdte/Gsh Core-Shell Quantum Dots |
| CN102004090A (en) * | 2009-11-30 | 2011-04-06 | 李芳� | Design of an off-on fluorescent molecular probe for selective recognition of Cd2+ |
| CN109738411A (en) * | 2019-01-31 | 2019-05-10 | 中南民族大学 | A kind of bionic array sensor and its application based on quantum dot fluorescence quenching |
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